TWI670292B - Polyamide resin and compact containing the same - Google Patents

Abstract

The present invention provides a polyamidamide resin which comprises a unit derived from ε-caprolactam and/or ε-aminohexanoic acid (hereinafter, referred to as "unit 1"), and a unit derived from a source of adipic acid. (hereinafter, this is also referred to as "unit 2"), and a unit derived from a self-diamine (hereinafter, referred to as "unit 3"), wherein the concentration of the amine group at the tail end of the polyamide resin is higher than that described above. The carboxyl group concentration at the tail end of the polyamide resin is larger, and the unit 1 is more than 60% by weight and less than 80% by weight with respect to the total amount of the unit 1, the unit 2, and the unit 3.

Description

Polyamide resin and molded article containing the same

The present invention relates to a polyamide resin and a molded article containing a polyamide resin.

The polyamide resin represented by the polyamide 6 , the polyamide 66 or the polyamide 12 is excellent in heat resistance and moldability, and is used as a raw material of a molded article such as a film for food packaging.

Patent Document 1 discloses a film for deep drawing packaging having a single layer or a multilayer polyimide film of at least one layer of a polyamide layer, and the polyamide layer contains 50 to 90% by weight. (A) a component selected from the group consisting of ε-caprolactam and ε-aminohexanoic acid, and (B) a component selected from the group consisting of 12-aminododecanoic acid and ω-lauric acid and (C) The total amount of the molar salt of the amine and adipic acid (the total amount of the B component and the C component) is 10 to 50% by weight of the copolymerization (including the A component, the B component, and the C component, and the total of the three components is Polyamine obtained by 100% by weight). Further, Patent Document 2 discloses a polyimide film having a single layer or a multilayered polyimide film having at least one layer of a polyamide layer, the polyamine layer being the aforementioned polyamine, and Manufactured by water-cooled expansion molding.

[Previous Technical Literature]

(Patent Literature)

Patent Document 1: Japanese Laid-Open Patent Publication No. 2006-111762

Patent Document 2: Japanese Laid-Open Patent Publication No. 2006-111763

The polyimide film described in Patent Document 1 is excellent in deep drawability in addition to excellent oxygen barrier properties and puncture properties, and the polyimide film described in Patent Document 2 is in addition to oxygen barrier properties. In addition to excellent puncture, even hot water shrinkage is large, and the shrinkage is also excellent, but depending on the use, depending on the packaging, there are still some shortcomings. Further, according to the study by the present inventors, the monofilaments of the polyamides described in Patent Documents 1 and 2 may have insufficient knot strength, transparency, and moldability. The object of the present invention is to provide superior film shrinkage, puncture strength and deep drawability after wet heat treatment, and to impart dough strength, transparency, tensile strength after wet heat treatment and formability of a monofilament. Polyamide resin.

The present inventors of the present invention have carefully studied again in order to solve the aforementioned problems, and as a result, have found that a specific amount of a source of its own indoleamine and/or aminocaproic acid unit, a source of adipic acid unit, and a source of its own diamine are contained. When the polyamine resin having a higher concentration of the amine group at the tail end than the carboxyl group at the tail end is used as a raw material of the molded article, there is a better film shrinkage property, and the puncture strength after the wet heat treatment and Deep stretched and has The present invention has been completed by the knot strength, transparency and formability of the monofilament.

The gist of the present invention is as follows.

The present invention relates to a polyamidamide resin containing a unit derived from ε-caprolactam and/or ε-aminohexanoic acid (hereinafter, also referred to as "unit 1"), and a source of adipic acid. The unit (hereinafter, referred to as "unit 2") and the unit derived from hexamethylene diamine (hereinafter, referred to as "unit 3"), wherein the tail of the polyamide resin The concentration of the terminal amine group is greater than the concentration of the carboxyl group at the tail end of the polyamine resin, and the unit 1 is more than 60% by weight and less than 80% by weight relative to the total amount of the unit 1, the unit 2 and the unit 3.

The present invention 2 relates to the polyamidamide resin of the present invention 1, which does not contain a unit derived from a component selected from 12-aminododecanoic acid and ω-lauric acid.

The present invention 3 relates to a polyamidamide resin according to the present invention 1 or 2 which is derived from a unit derived from ε-caprolactam and/or ε-aminohexanoic acid (hereinafter, this is also referred to as "unit 1" The unit derived from the self-diacid (hereinafter, referred to as "unit 2") and the unit derived from the self-diamine (hereinafter, referred to as "unit 3").

The present invention relates to the polyamidamide resin according to any one of claims 1 to 3, wherein the polyamine resin is in a 96% by weight sulfuric acid, a polyamine concentration of 1% by weight, and a temperature of 25 °C. The relative viscosity (η r) measured was 3.4 or more.

The present invention 5 relates to the polyamidamine resin according to any one of the inventions 1 to 4, wherein the tail amine group concentration is from 2.30 to 3.30 × 10 ^-5 eq/g.

The present invention is the polyamido resin according to any one of claims 1 to 5, wherein the terminal carboxyl group concentration is 2.00 to 3.00 × 10 ^-5 eq/g.

The present invention is the polyamidamide resin according to any one of the inventions 1 to 6, wherein the difference between the tail amine group concentration and the terminal carboxyl group concentration is 0.05 to 1.0 × 10 ^-5 eq/g.

The present invention 8 relates to a molded article comprising the polyamidamide resin according to any one of the items 1 to 7 of the present invention.

The present invention 9 relates to an unstretched film comprising the polyamidamide resin according to any one of the items 1 to 7 of the present invention.

The present invention 10 relates to an extended film which is obtained by extending the unstretched film of the present invention 9.

The present invention 11 is an unstretched film according to the invention 9, which is a film for food packaging.

The present invention 12 is an extended film relating to the present invention 10 which is a film for food packaging.

The present invention 13 relates to an unextended laminate film comprising the unstretched film of the present invention 9.

The present invention 14 relates to an extended laminated film comprising the stretched film of the present invention 10.

The present invention 15 relates to a polyamidamine monofilament comprising the polyamidamine resin according to any one of the items 1 to 7 of the present invention.

According to the present invention, it is possible to provide more excellent film shrinkage, puncture strength and deep drawability after wet heat treatment, and imparting knot strength, transparency, tensile strength and formability after wet heat treatment with monofilament A polyamide resin of the molded article.

In this specification, the words in "steps" include not only independent steps, but also situations that cannot be clearly distinguished from other steps. If the intended purpose of this step is achieved, it is deemed to be included in the language. The meaning. Further, the numerical range indicated by "to" indicates a range in which the numerical values described before and after "to" are included as the minimum value and the maximum value, respectively. Further, when the content of each component in the composition is plural in the presence of the respective components in the composition, unless otherwise stated, it means the total amount of the plurality of substances present in the composition.

[Polyuramine resin]

The polyamide resin contains a unit derived from ε-caprolactam and/or ε-aminohexanoic acid (hereinafter referred to as "unit 1") and a unit derived from adipic acid (hereinafter, this is used). Also known as "unit 2"), and a polyamine resin of a unit derived from a self-diamine (hereinafter, referred to as "unit 3"), wherein the polyamine resin has a tail amine group concentration as compared with the foregoing The concentration of the carboxyl group at the tail end of the polyamide resin is larger, and the unit 1 is more than 60% by weight and less than 80% by weight with respect to the total amount of the unit 1, the unit 2, and the unit 3.

The content ratio of the unit 1 to the total amount of the unit 1, the unit 2, and the unit 3 is more than 60% by weight and less than 80% by weight, preferably 62 to 78% by weight, more preferably 65 to 75% by weight. Unit 1 content rate When it is 80% by weight or more, the shrinkability and deep drawability of the film are deteriorated. Moreover, when the content rate of the unit 1 is 80% by weight or more, the monofilament cannot obtain sufficient nodule strength and the transparency is inferior. On the other hand, when the content of the unit 1 is 60% by weight or less, the puncture strength of the film, in particular, the puncture strength after the wet heat treatment is inferior. Moreover, the tensile strength of the monofilament is remarkably lowered, and there is no practicality. When the content of the unit 1 is 62% by weight or more, the puncture strength tends to be further improved, and when it is 78% by weight or less, the shrinkability and the deep drawability tend to be improved. Further, if it is in this range, it is expected that a monofilament having a high knot strength will be obtained.

The content ratio of the unit 2 and the unit 3 is not particularly limited. The content of the unit 2 is preferably 45 to 55 mol%, more preferably 47 to 53 mol%, still more preferably 49 to 51 mol%, based on the total number of moles of the unit 2 and the unit 3. More preferably, it is preferably 50% by mole. That is, the unit 2 and the unit 3 are particularly preferably present.

The polyamine resin may further contain a unit derived from a raw material of another polyamide resin other than the unit 1, the unit 2, and the unit 3 as long as the effect of the present invention is not impaired (hereinafter, this is also referred to as "Other units"). The raw material of the other polyamide resin is not particularly limited, and examples thereof include a lactam, an aminocarboxylic acid, a salt of a diamine and a dicarboxylic acid (nylon salt), or a mixture of a diamine and an oxalic acid diester. . The raw material of the other polyamide resin does not contain ε-caprolactam, ε-aminohexanoic acid, adipic acid, and hexamethylenediamine.

Examples of the indoleamines include ω-heptaneamine, ω-undecane decylamine, ω-lauryl decylamine, α-pyrrolidone, α- Piperidone and the like.

Examples of the aminocarboxylic acid group include aliphatic ω- such as 7-amino heptanoic acid, 8-aminooctanoic acid, 9-amino decanoic acid, 10-amino decanoic acid, and 11-aminoundecanoic acid. Aminocarboxylic acid.

Examples of the dicarboxylic acid system include oxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, sebacic acid, sebacic acid, undecanedioic acid, and dodecane diene. Aliphatic dicarboxylic acid such as acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecandioic acid, octadecanedioic acid, eicosanedioic acid, etc., 1,3-/ An alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid, dicyclohexanemethane-4,4'-dicarboxylic acid or norbornane dicarboxylic acid, isophthalic acid or terephthalic acid An aromatic dicarboxylic acid such as 1,4-/1,8-/2,6-/2,7-naphthalenedicarboxylic acid or the like.

Examples of the oxalic acid diester system include dimethyl oxalate, diethyl oxalate, di-n-(iso)propyl oxalate, and di-n-oxalate (or different or 2) ethylenediester diester of an aliphatic alcohol such as butyl ester, oxalic acid diester of an alicyclic alcohol such as dicyclohexyl oxalate, and ethylene glycol of an aromatic alcohol such as diphenyl phthalate Acid diester.

In addition to hexamethylenediamine, the diamine system is exemplified as the polymerization regulator described later.

The polyamide resin is preferably one which does not contain a unit derived from 12-aminododecanoic acid and ω-lauric acid, and more preferably contains no other unit. When the polyamide resin is a unit containing no 12-aminododecanoic acid and ω-lauric acid, the oxygen permeability coefficient of the molded article of the polyamide resin tends to be low. Also, the polyamide resin is in the absence of other units. At the time, there is a tendency that the polyamide resin can be produced more easily.

The polyamide resin may also have a unit derived from a polymerization regulator which can be used in the production of a polyamide resin. Examples of the polymerization regulator include ethylenediamine, propylenediamine, butanediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, decanediamine, and undecanediamine. , dodecanediamine, tridecanediamine, tetradecanediamine, stearyldiamine, nonadecanediamine, eicosanediamine, 2-/3-methyl-1,5-pentyl Alkyldiamine, 2-methyl-1,8-octanediamine, 2,2,4-/2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1 , an aliphatic diamine such as 9-decanediamine; 1,3-/1,4-cyclohexanedimethylamine, bis(4-aminocyclohexyl)methane, bis(4-aminocyclohexyl) Propane, bis(3-methyl-4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)propane, 5-amino-2,2,4-trimethyl- 1-cyclopentylmethylamine, 5-amino-1,3,3-trimethylcyclohexylmethylamine (isophorone diamine), bis(aminopropyl)perazine Bis(aminoethyl)per An alicyclic diamine such as norbornane dimethylamine or tricyclodecane dimethylamine; or an aromatic diamine such as m-/p-xylenediamine. These may be used alone or in combination of two or more.

In the polyamine resin, the content ratio of the unit 1, the unit 2, and the unit 3 in the case where the polymerization regulator unit is not present, and the unit 1, unit 2, and unit 3 in the case where the polymerization regulator unit is present The content of the unit derived from the polymerization regulator is not particularly limited, but is preferably 95% by weight or more, more preferably 99% by weight or more, and still more preferably 100% by weight. Further, in the polyamide resin, the content ratio of the other unit is 100% by weight minus the content ratio or unit of the unit 1, the unit 2, and the unit 3 described above. 1. The value of the content of the unit 2, unit 3 and the polymerization regulator unit.

The content of the polymerization regulator unit in the polyamide resin is not particularly limited, but is preferably from 120 to 970 ppm, more preferably from 120 to 10,000 ppm by weight based on the total amount of the unit 1, the unit 2, and the unit 3. To 690ppm. When the polymerization regulator is hexamethylenediamine, the content of the unit 3 is the content of the unit of the source self-diamine used as the polymerization regulator.

The content of each unit in the polyamide resin can be measured by gas chromatography after the polyamine resin is hydrolyzed with hydrochloric acid and then subjected to esterification or imidization. Further, the content ratio of each unit in the raw material components of each unit in the polyamide resin is almost equal.

Thus, in the case of a polyamide resin, a polyamine resin containing unit 1, unit 2 and unit 3 and containing no unit derived from 12-aminododecanoic acid and ω-lauric acid is preferred. And/or a polyamido resin containing unit 1, unit 2, unit 3 and a unit derived from a polymerization regulator, and containing no unit derived from 12-aminododecanoic acid and ω-lauric acid, Particularly preferred is a polyamide resin composed of unit 1, unit 2, and unit 3, and/or a polyamide resin composed of unit 1, unit 2, unit 3, and a unit derived from a polymerization regulator (ie, contains Unit 1, unit 2 and unit 3, and containing no polyamine resin of other units and/or polyamine resin containing unit 1, unit 2, unit 3 and unit derived from polymerization regulator, and containing no other unit ).

(end base concentration)

The concentration of the amine group at the tail end of the polyamide resin is larger than the concentration of the carboxyl group at the tail end. tail When the terminal amine group concentration is below the terminal carboxyl group concentration, the puncture strength after the wet heat treatment is lowered.

The concentration of the amine group at the tail end of the polyamide resin of the present invention is not particularly limited as long as it is larger than the carboxyl group concentration at the tail end of the polyamide resin of the present invention. The tail amine group concentration is preferably from 2.30 to 3.30 × 10 ^-5 eq/g, more preferably from 2.50 to 3.00 × 10 ^-5 from the viewpoint of the puncture strength of the film after the wet heat treatment and the tensile strength of the monofilament. Eq/g. Further, the concentration of the terminal carboxyl group of the polyamide resin of the present invention is not particularly limited as compared with the concentration of the amine group at the tail end of the polyamide resin of the present invention. The terminal carboxyl group concentration is preferably from 2.00 to 3.00 × 10 ^-5 eq/g, more preferably from 2.20 to 2.80 × 10 ^-5 eq/g, from the viewpoint of puncture strength and tensile strength after the wet heat treatment. The difference between the tail amine group concentration and the terminal carboxyl group concentration of the polyamide resin of the present invention is preferably from 0.05 to 1.0 × 10 ^-5 eq / from the viewpoint of puncture strength and tensile strength after the wet heat treatment. g, more preferably 0.10 to 0.70 × 10 ^-5 eq/g, still more preferably 0.10 to 0.50 × 10 ^-5 eq/g.

The concentration of the amine group at the tail end is obtained by dissolving the polyamidamide resin in a mixed solution of phenol and methanol, and titrating with 0.05 N hydrochloric acid. Further, the concentration of the terminal carboxyl group was determined by dissolving the polyamidamide resin in benzyl alcohol and titrating with a 0.05 N sodium hydroxide solution.

(relative viscosity)

The polyamidamide resin is a relative viscosity measured under conditions of a polyamine concentration of 1% by weight and a temperature of 25 ° C in 96% by weight of sulfuric acid according to JIS K-6920, preferably 3.4 or more, more preferably 3.4 to 5.0, and more preferably 4.0 to 4.8. The relative viscosity is only 3.4 or more, and the polyamide resin is melted. The viscosity at the time is appropriate, the molding is easy, and the molded article containing the polyamide resin can be imparted with good mechanical properties.

(melting point)

The melting point of the polyamide resin is not particularly limited, and is preferably more than 173 ° C and less than 192 ° C, more preferably 174 to 191 ° C. When the melting point exceeds 173 ° C, the puncture strength tends to increase, and if it does not reach 192 ° C, the shrinkage property and the deep drawability tend to be improved. The melting point can be determined by DSC (differential scanning calorimetry).

(Method for producing polyamine resin)

The polyamide resin can be melt-polymerized, solution-polymerized, and solid-phase by using ε-caprolactam, ε-aminocaproic acid, adipic acid, hexamethylenediamine, and optionally other polyamide resins. A known method such as polymerization is obtained by polymerization. Here, as the raw material of adipic acid and hexamethylenediamine, a salt of 50 mol% of hexamethylenediamine and 50 mol% of adipic acid (AH salt) can also be used. Depending on the production method and the production apparatus, there may be cases where the volatilization of the raw materials, the reaction, and the like are different, and in the polyamide resin, it is preferred to be a polyamine resin having the contents of the above-mentioned unit 1, unit 2, and unit 3. Ways to adjust the amount of raw materials in each unit.

A polymerization regulator can also be used in the polymerization. The polymerization regulator is used, that is, it is possible to adjust the tail amine group concentration and the terminal carboxyl group concentration of the polyamide resin. The amount of the polymerization regulator may vary depending on the production method and the production apparatus of the polyamide resin, such as volatilization and reaction of the polymerization regulator. The guanamine resin is preferably adjusted so as to be a content of a unit derived from the polymerization regulator.

Further, a catalyst may be used during the polymerization (for example, phosphoric acid, phosphorous acid, hypophosphorous acid or a salt thereof). The pressure at the time of polymerization may also be normal pressure, reduced pressure, pressure, or a combination thereof.

The apparatus for producing the polyamide resin is not particularly limited, and examples thereof include a batch reactor, a single-tank or multi-tank continuous reaction apparatus, a tubular continuous reaction apparatus, a uniaxial kneading extruder, and a biaxial type kneading extruder. A kneading reaction extruder such as a machine.

[Polyuramine resin composition]

When the polyamide resin is used, the additive may be used in combination as long as the effects of the present invention are not impaired. Therefore, the present invention also relates to a polyamide resin composition containing a polyamide resin (hereinafter also referred to simply as "polyamide resin composition"). The polyamide resin composition is preferably a polyamine resin composition for producing a molded article, more preferably a polyimide resin composition for forming a film (polyamide resin composition for a film).

The polyamide resin composition of the present invention may contain an additive or a thermoplastic resin other than the polyamide resin of the present invention as long as the effects of the present invention are not impaired. The additive is not particularly limited as long as it is a component which is usually contained in the composition of the molded article for producing a polyamide resin, and examples thereof include a thermal stabilizer, an antioxidant, an ultraviolet absorber, a weathering agent, a lubricant, a filler, and a crystal. Nuclear agents, plasticizers, foaming agents, anti-blocking agents, anti-fogging agents, flame retardants, colorants (pigments, dyes) Materials, etc.), stabilizers, coupling agents, etc. These may be appropriately selected depending on the purpose.

In the polyamide resin composition, the polyamine resin content of the present invention is preferably from 50 to 100% by weight, more preferably from 70 to 100% by weight, particularly preferably from 90 to 100% by weight. When the polyamine resin content of the present invention is 50% by weight or more, the properties as a polyamide resin can be further exhibited. Further, the content of the additive in the total amount of the polyamide resin composition or the thermoplastic resin other than the polyamide resin of the present invention is a value obtained by subtracting the content of the polyamide resin from 100% by weight.

Therefore, the present invention is a polyamide resin composition comprising a polyamide resin and an additive, wherein the polyamine resin composition preferably has a polyamine resin content of 50 to 100% by weight.

The polyamide resin composition can be prepared by melt-kneading each component. The method of melt kneading is not particularly limited, and it can be carried out using a kneading machine such as a uniaxial extruder, a twin screw extruder, a kneader, or a banbury mixer. Further, each component may be mechanically blended by a mixer or the like.

[Molded product containing polyamide resin]

The molded article containing a polyamide resin is a molded article of a polyamide resin or a molded article of a composition comprising a superpolyamine resin. The polyamide resin and the polyamide resin composition can be formed into a molded article by a molding process such as injection, extrusion, or extrusion. The molded article containing a polyamide resin can be used in a molded article of a conventional polyamide resin or a polyamide resin composition. In addition to automotive components, computers and related machines, optical machines In addition to molded articles for a wide range of applications such as components, electric/electronic equipment, information/communication equipment, precision equipment, civil engineering/construction supplies, medical supplies, and household goods, monofilaments, fibers, films, and the like are preferred. It is a film and a monofilament. When the molded article is a film, the film has both good shrinkability, puncture strength after heat treatment, and deep stretchability. Further, when the molded article is a monofilament, the monofilament has both knot strength, transparency, and formability. Hereinafter, a description will be given of a film containing a polyamide resin (hereinafter also referred to simply as "polyamide film") and a monofilament (hereinafter also referred to as "polyamine monofilament") in a preferred embodiment of the present invention. .

(polyamide film)

The film containing the polyamide resin may, for example, be a film comprising a polyamide resin and a film comprising a polyamide resin composition, and is preferably a film comprising a polyamide resin. The polyamidamide film containing the polyamide resin may be an unstretched polyamide film or an extended polyamine film obtained by extending the unstretched polyamide film.

<Unstretched Polyamide Film>

The unstretched polyamide film is obtained by a known film production method using a polyamide resin and a polyamide resin composition. Examples of the known film production method include a T-die molding method, an air-cooling blow molding method, and a water-cooling blow molding method. The film produced is essentially an unoriented, unstretched film.

<<Characteristics of Unstretched Polyamide Films>>

The deep drawing degree of the unstretched polyamide film is not particularly limited, but is preferably more than 50.0 mm, more preferably more than 50.0 mm and less than 75.0 mm, still more preferably 52.0 to 74.0 mm, and particularly preferably 60.0 to 72.5. Mm. When the deep drawing degree exceeds 50.0 mm, the formability is improved, whereby a large amount and a large amount of food can be deeply drawn and stretched, and a variety of molds can be used.

Unstretched polyamide film oxygen permeability coefficient is not particularly limited, preferably less than 31.0cc / m ² ‧day‧atm is, more preferably more than 26.0cc / m ² ‧day‧atm to 30.0cc / m ² ‧ Below day‧atm, it is more preferably 27.0 to 28.0 cc/m ² ‧day‧atm. If the oxygen permeability coefficient of the unstretched polyamidamide film is less than 31.0 cc/m ² ‧day ‧ atm, the oxygen which is the biggest cause of deterioration of food oil, discoloration, mold generation, and aerobic bacteria can be effectively covered. Broken.

<Extended Polyamide Film>

The extended polyamine film is obtained by a known film stretching method using an unstretched polyimide film. Further, in the production of the extended polyimide film, the production of the unstretched polyimide film can be continued and the stretching method can be continuously carried out, or the unstretched polyamide film can be produced and rolled into a roll shape, and the stretching can be carried out in another step. method.

The stretching method is not particularly limited, and examples thereof include a uniaxial stretching of a heating roller, a simultaneous biaxial stretching by a blown film method, and a sequential biaxial stretching method by a heating roller and a tenter. The temperature of the heating roller is not particularly limited and may be set in the range of 50 ° C to 130 ° C, and is responsive to polyamine The material of the film and the stretching ratio of the purpose can be appropriately selected. The stretching ratio is the stretching ratio of the extrusion direction (MD) of the film and the direction perpendicular to the extrusion direction of the film (TD). The stretching ratio in the extrusion direction of the film is not particularly limited, but is preferably 2 times or more, more preferably 2 to 6 times, and particularly preferably 2.5 to 5 times. The stretching ratio in the direction perpendicular to the film extrusion direction is not particularly limited, but is preferably 2 times or more, more preferably 2 to 6 times, and particularly preferably 2.5 to 5 times. The extension ratio can be adjusted according to the purpose.

<<Extension of Polyamine Films>>

The shrinkage property of the extended polyimide film is preferably 40% or more, more preferably 41 to 60%, as measured by a hot water shrinkage test of the film at 90 ° C for 1 minute, particularly preferably 42 to 55%. When the heat shrinkage rate is 40% or more, when the food is shrink-wrapped, the adhesion between the food and the film is improved, and the gap between the food and the film tends to be extremely lowered. When voids between the food and the film are present, the air present in the voids may promote the deterioration of the food. In particular, even if it is a heterogeneous food or the like (for example, crab, lobster, etc.), as long as the heat shrinkage rate is 40% or more, voids are less likely to occur between the food and the film.

When the stretching ratio of the stretched polyamide film becomes large, the heat shrinkage rate tends to increase. Therefore, the heat shrinkage rate of the above-mentioned extended polyamide film is preferably 2.5 to 4.0 times (2.5×2.5 to 4.0×4.0 times) of the stretching ratio of the extrusion direction and the extrusion direction of the film. The heat shrinkage ratio of the guanamine film is more preferably from 3.0 × 3.0 to 3.5 × 3.5 times the heat shrinkage ratio of the extended polyamide film.

The shrinkage property can be measured by the method of "5)" in the examples described later.

In the wet heat treatment for extending the polyamide film, the puncture strength after 10 days of treatment at a constant temperature of 80 ° C and 90% RH is preferably 12 N or more, and more preferably 12 to 14 N. When the piercing strength of the stretched film is less than 12 N, when the food such as crab, shrimp, lobster or the like is shrunk, the film may be broken due to the protrusion of the food. In addition, the puncture strength in the case where the heat-expanded polyimide film is not subjected to the heat treatment immediately after the production is not particularly limited, and may be, for example, 12 N or more, and preferably 13 to 15 N.

<thickness>

The thickness of the polyamide film is not particularly limited and may be selected depending on the application. In the case of a single-layer film comprising a polyimide film, the thickness of the polyimide film is preferably from 10 to 150 μm, more preferably from 10 to 100 μm, still more preferably from 10 to 80 μm.

[Laminated film containing polyimide film]

The polyamide film has both excellent deep drawability, shrinkability, and puncture strength after wet heat treatment, but may contain other layers as long as the effects of the present invention are not impaired. Accordingly, the present invention is also directed to a laminated film comprising a polyimide film.

The extended state of the laminated film can be selected in accordance with the extended state of the polyimide film. That is, the polyamide film is an unstretched polyamide film. In the case of a laminate film containing a polyimide film (hereinafter, a laminated film containing a polyimide film is also referred to as a "layered film"), an unlaminated laminated film is used. Further, when the polyamide film is a polyamide film, the laminate film is an extended laminate film. The method for producing the laminated film may be a method comprising the steps of including one side of the polyimide film or other layers of the two-layer layer. The method of the lamination is not particularly limited, and examples thereof include a co-extrusion method, an extrusion lamination method, a dry lamination method, and the like described in JP-A-2011-225870, and from the viewpoint of economy, coextrusion is preferred. law.

(other layers)

The laminated film is not particularly limited as long as it can exhibit the effect of the polyimide film, and examples thereof include a thermoplastic resin layer and an adhesive resin layer. Here, the adhesive resin layer is appropriately selected for the purpose of improving the adhesion and formability of the polyamide layer and the thermoplastic resin layer.

The thermoplastic resin layer is a layer containing a thermoplastic resin, specifically, a layer containing a thermoplastic resin or a thermoplastic resin composition containing a thermoplastic resin (hereinafter, a thermoplastic resin containing a thermoplastic resin) The layer is also referred to as a "thermoplastic resin composition". Specifically, the thermoplastic resin composition contains a composition of a thermoplastic resin and an additive.

Examples of the thermoplastic resin include non-polar polyolefins (for example, low-density polyethylene, linear low-density polyethylene, ethylene-α-olefin copolymer having 3 to 8 carbon atoms, propylene homopolymer, propylene and carbon). 4 to 8 copolymers of α-olefins, etc.), ionic polymers, ethylene-acrylic acid Copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, ethylene-methacrylic acid copolymer, polyester, polyvinyl alcohol, and the like. Thermoplasticity can also be thermally fused. Examples of the thermoplastic resin having such thermal fusion properties include low density polyethylene, linear low density polyethylene, ethylene-a-olefin copolymer having 3 to 8 carbon atoms, ionic polymer, and ethylene. Acrylic copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, ethylene-methacrylic acid copolymer.

The thermoplastic resin is preferably a non-polar polyolefin, an ethylene-vinyl acetate copolymer or a thermoplastic resin having heat-melting properties. When the thermoplastic resin is a non-polar polyolefin, the water vapor barrier property of the laminated film tends to be improved. When the thermoplastic resin is a layer of an ethylene-vinyl acetate copolymer, the polyamine film tends to have a lower oxygen permeability. When the thermoplastic resin is a thermoplastic resin having heat-melting properties, when the polyimide film is used as a film for deep-drawing packaging, the heat-melting temperature of the lid member for deep-drawing packaging can be lowered as much as possible. This production efficiency has a tendency to increase.

The following resin layer is a layer containing an adhesive resin, and specifically includes a layer containing an adhesive resin or an adhesive resin composition containing an adhesive resin (hereinafter, an adhesive resin composition containing an adhesive resin is also used) A layer called "adhesive resin composition"). Specifically, the adhesive resin composition contains a composition of an adhesive resin and an additive. The resin to be further modified is, for example, an oxygen-modified polyolefin resin such as an oxygen-modified polyethylene obtained by grafting at least one monomer selected from an unsaturated carboxylic acid or a derivative thereof.

The additive contained in the thermoplastic resin composition and the adhesive resin composition is exemplified by the above additives in the polyamide resin composition.

<layer composition>

The specific layer structure of the laminated film may be exemplified by two layers of a polyimide film and a thermoplastic resin layer, three layers of a polyamide film/adhesive resin layer/thermoplastic resin layer, and a polyamide film. At least three or more layers of one or more other layers selected from the group consisting of a polyamide film, an adhesive resin layer, and a thermoplastic resin layer; and a polyimide layer, a thermoplastic resin layer, and a thermoplastic resin layer; The adhesive resin layer is at least four or more layers selected from the group consisting of a polyimide film, an adhesive resin layer, and a thermoplastic resin layer. Specific examples thereof include a polyamide film/adhesive resin layer/thermoplastic resin layer, a polyamide film/adhesive resin layer/thermoplastic resin layer/adhesive resin layer/thermoplastic resin layer, and a thermoplastic resin. Layer/adhesive resin layer/polyimine film/adhesive resin layer/thermoplastic resin layer or the like. Here, the adhesive resin layer may be provided as needed. Further, when the laminated film is an unstretched laminated film and is a film for deep drawing, it is preferred to have a thermoplastic resin layer in the inner layer. Here, the layer in contact with the outside air in the laminated film is an outer layer, and the layer in contact with the food of the packaged article is an inner layer.

<thickness>

The thickness of the laminated film is not particularly limited and can be selected depending on the application. The thickness of each layer of the polyimide film in the laminated film is preferably from 2 to 100 μm, more preferably from 5 to 80 μm. The thickness of each layer of the thermoplastic resin layer can be appropriately selected depending on the purpose, and is preferably in the range of 8 to 120 μm, for example. The thickness of each layer of the subsequent resin layer can be selected depending on the purpose, and is preferably in the range of 1 to 100 μm, for example. The total film thickness of the laminated film is not particularly limited, and is preferably from 5 to 500 μm, more preferably from 20 to 300 μm, particularly preferably from 50 to 200 μm.

(polyamide monofilament)

The polyamidamine monofilament containing a polyamide solvent may, for example, be a polyamine monofilament comprising a polyamide resin and a polyamine monofilament comprising a polyamide resin composition, and a poly-melamine resin-containing polymer. Amidoxime monofilament is preferred.

The diameter of the polyamide monofilament is not particularly limited, but is preferably from 0.5 to 20 mm, more preferably from 1 to 5 mm.

Polyamine monofilaments are obtained by a known monofilament production method using a polyamide resin and a polyamide resin composition. The method for producing a known monofilament is, for example, a pellet of a polyamide resin which is melted by an extruder or the like and extruded from a spinning nozzle, and cooled in a refrigerant bath such as water or trichloroethylene. A method of making an unstretched filament. At this time, it is preferable that the distance from the wire outlet of the spinning nozzle to the liquid surface of the refrigerant is maintained at about 10 to 300 mm.

The unstretched filaments can be further extended and thermally fixed. Here, the extension is preferably a two-stage extension in two stages.

The extension of the first stage of the 2-stage extension, either in water vapor or in heat The unstretched filaments are extended to 2 to 5 times in water, preferably to 3 to 4 times. If the stretching ratio is in this range, the knot strength tends to be higher.

When extending in water vapor, it is preferably in the range of 95 to 120 ° C, and more preferably in the range of 100 to 110 ° C. When the temperature of the water vapor is within this temperature range, the knot strength and transparency of the obtained monofilament tend to be improved.

When extending in hot water, the temperature of the hot water is preferably in the range of 50 to 95 ° C, more preferably in the range of 60 to 90 ° C. When the temperature of the hot water is within this temperature range, the knot strength and transparency of the obtained monofilament tend to be improved.

In the gaseous environment, the extension of the second stage is preferably carried out by 1.1 to 2.5 times, and more preferably by 1.2 to 2.5 times. The gas is not particularly limited, and examples thereof include an inert gas such as helium, nitrogen, or argon, or air. The temperature of the substrate environment in the extension of the second stage is preferably in the range of 180 to 300 ° C, more preferably in the range of 120 to 250 ° C. When the extension of the second stage is the above temperature range and the stretching ratio, the knot strength and transparency of the obtained monofilament tend to be improved.

The monofilament extended in two stages is preferably heat-fixed. The monofilament extended in two stages can be thermally fixed in a gas atmosphere of preferably 160 to 320 ° C, more preferably 160 to 350 ° C while relaxing at 0 to 10% on one side. When it is in this temperature range, the knot strength tends to increase.

In the above 2-stage stretching and heat treatment, the total extension ratio is 4.0 to 7.0, preferably 4.5 to 6.5, more preferably 5.5 to 6.0. range.

The polyamine monofilament is a non-stretched yarn produced from polyamine, and is subjected to two-stage stretching and heat treatment to produce a monofilament having a diameter of about 0.5 to 20 mm and excellent in transparency, moldability, and knot strength.

[use]

The polyamide resin and the polyamide resin composition can be used as a raw material of a molded article. A molded article containing a polyamide resin, that is, a molded article comprising a polyamide resin and a molded article comprising a polyamide resin composition, can be used for a molded article of a conventional polyamide resin and a polyamide resin composition. It can also be used in food packaging films, automotive components, computers and related equipment, optical equipment components, electrical/electronic equipment, information/communication equipment, precision machinery, civil engineering/construction supplies, medical supplies, household goods, etc. Among the applications of the van, it is particularly advantageous for films for food packaging.

The unstretched polyamide film is a raw material that can be used as an extended polyimide film.

The unstretched polyamide film and the unstretched laminated film are excellent in deep drawability, and can be suitably used as a film for food packaging, particularly a film for deep drawing of foods. When the unstretched polyimide film is used as a film for deep drawing, the food is stored in a substrate for deep drawing obtained by deep drawing the film, and is packaged using a lid material. The foodstuff contained in the substrate for deep-drawing packaging is, for example, a food sliced into a sheet shape such as ham or cheese. The cover material is not particularly limited and may be appropriately selected depending on the purpose.

The deep drawing forming method of the unstretched polyamide film and the unstretched laminated film is not particularly limited, and examples thereof include vacuum forming and pressure forming. A food packaging method using a film for deep drawing packaging is a step of using a substrate for deep drawing packaging obtained by deep drawing of a film for deep drawing packaging, and a step of accommodating a food, and bonding the substrate The sealing step with the cover material can be carried out using a continuous or batch type device. The deep drawing molding conditions are not particularly limited and may be selected depending on the thickness and purpose of the film. The molding temperature is not particularly limited, and is preferably 60 to 130 °C.

The extended polyamide film and the extended laminated film are excellent in hot water shrinkage and excellent in oxygen barrier properties, and are therefore advantageous for food packaging films, such as shrink film for food packaging; for filling or packaging sausages, etc. It is useful for the use of a casing film for food packaging such as a liquid food, processed meat, or a solid food such as ham.

Polyamine monofilament can be used as a structure for filaments, multifilaments, and nets for fishery, industrial, clothing, medical, and the like.

[Examples]

Hereinafter, the present invention will be described by way of examples and comparative examples, but the present invention is not limited to the following examples. The measured values shown in Tables 1 and 2 were measured by the following methods.

1) Relative viscosity: According to JIS K 6810, 96% by weight of concentrated sulfuric acid was used as a solvent, and a concentration of polyamine resin of 1% by weight was measured at a temperature of 25 ° C using a Ubbelohde viscometer.

2) Melting point: using DSC 210 type manufactured by Seiko Instruments Co., Ltd., The polyamine resin was heated to 250 ° C at a heating rate of 10 ° C / min under a nitrogen atmosphere, and after maintaining at this temperature for 10 minutes, it was kneaded at a rate of 10 ° C / minute to 30 ° C, and then again at 10 ° C / The temperature was heated to 250 ° C in a minute, and the heating temperature at the endothermic peak obtained by the reheating process was taken as the melting point.

3) tail end group concentration: the tail end group concentration of the amine group (-NH ₂ ) in the polyamidamide resin, the polydecylamine resin is dissolved in benzyl alcohol, and titrated with a 0.05 N sodium hydroxide solution. The concentration of the terminal group of the carboxyl group (-COOH) was measured by dissolving the polyamine resin in benzyl alcohol and titrating with a 0.05 N sodium hydroxide solution.

4) Unit content rate: The content ratio of the unit 1, the unit 2, and the unit 3 in the polyamide resin is obtained by hydrolyzing the polyamine resin with hydrochloric acid, followed by esterification and imidization, and the composition is used. Determined by gas chromatography analysis.

5) Shrinkage (hot water shrinkage ratio): The length A (mm) of the extrusion direction at the time of forming the T-die of the biaxially stretched film after the molding instant was measured, and the same film was immersed in a water bath set to 90 ° C. After a minute, the mixture was allowed to stand in an environment of 23 ° C and 50% RH for 24 hours, and the length B (mm) of the same place after the immersion was measured, and the hot water shrinkage ratio (%) was calculated according to the following formula (1).

Hot water shrinkage rate (%) = (A-B) / A × 100 (1)

6) Puncture strength: Measured at a piercing speed of 50 mm/min, 23 ° C, and 50% RH using a TENSILON UTM-III-200 manufactured by TOYO BALDWIN Co., Ltd. according to JAS P1019. The measurement is for the coaxial biaxially stretched film after the forming instant, and as the wet heat treatment The coaxial biaxially stretched film was treated at 80 ° C, 90% RH in a constant temperature, constant humidity chamber for 10 days.

7) Oxygen Permeation Coefficient: The oxygen permeability coefficient of the 50 μm unstretched film was measured under the conditions of 23 ° C and 0% RH according to ASTM D-3985-81 using MOCON-OX-TRAN 2/20 manufactured by Modern Control.

8) Depth of stretching (mm): Using a vacuum forming apparatus, PLAVAC TV-33, manufactured by Sanwa Industrial Co., Ltd., at a deep drawing temperature of 80 ° C, a preheating time of 120 seconds, and a vacuum of 20 Torr, the obtained 50 μm was not obtained. Deep drawing of the stretch film. The maximum depth (mm) which was not broken when formed under the foregoing conditions was taken as the stretching depth.

(Example 1: Production of Polyamine Resin (PA-1))

Into a 70 L autoclave, 15.0 kg of ε-caprolactam and a salt of AH salt (a salt obtained by adding a molar amount of adipic acid such as hexamethylenediamine to an aqueous solution of hexamethylenediamine) (50 wt% aqueous solution) were added. 10.0 kg and 2.0 kg of distilled water, 9.39 g of a hexanediamine aqueous solution (80 wt% aqueous solution) (hereinafter referred to as "HMD aqueous solution") as a polymerization regulator was added, and the inside of the polymerization tank was replaced with nitrogen gas, and then sealed and heated. The temperature in the polymerization tank was adjusted to 17.5 kgf/cm ² G at 180 ° C while stirring, and the temperature in the polymerization tank was raised to 240 ° C. After the polymerization temperature reached 240 ° C for 2 hours, the pressure in the polymerization tank was lowered to a normal pressure for about 2 hours. After the pressure reduction, after polymerization for 1 hour under a nitrogen gas stream, the pressure reduction polymerization was carried out for 2 hours. After introducing nitrogen gas and returning to normal pressure, the agitator was stopped, and the tow was pulled out to be pelletized. The polyamide particles were placed in boiling water, and after stirring for about 12 hours, the unreacted monomers after washing were extracted and removed, and then dried under reduced pressure at 100 ° C for 24 hours. The polyamidamide resin thus obtained had a relative viscosity of 4.55 and a melting point of 183 °C. This polyamine resin is referred to as PA-1.

(Example 2: Production of Polyamine Resin (PA-2))

14.0 kg of ε-caprolactam and 12.0 kg of AH salt aqueous solution (50 wt% aqueous solution) were added to a 70 L autoclave, and 8.56 g of an aqueous HMD solution as a polymerization regulator was added, and the same method as in Example 1 was carried out to obtain a relative viscosity. 4.66, polyamine resin with a melting point of 178 ° C. This is called polyamine resin PA-2.

(Example 3: Production of Polyamine Resin (PA-3))

Into a 70 L autoclave, 13.0 kg of ε-caprolactam, 14.0 kg of an aqueous solution of AH salt (50 wt% aqueous solution), and 4.97 g of an aqueous solution of HMD as a polymerization regulator were added, and the same method as in Example 1 was carried out to obtain a relative viscosity. 4.06, polyamine resin having a melting point of 176 °C. This is called polyamine resin PA-3.

(Comparative Example 1: Production of Polyamine Resin (PA-4))

Into a 70 L autoclave, 16.0 kg of ε-caprolactam and 8.0 kg of an aqueous solution of AH salt (50 wt% aqueous solution) were added, and 11.04 g of an aqueous HMD solution as a polymerization regulator was added, and the same method as in Example 1 was carried out to obtain a relative viscosity. 4.44, a polyamide resin having a melting point of 192 ° C. This is called polyamine resin PA-4.

(Comparative Example 2: Production of Polyamine Resin (PA-5))

12.0 kg of ε-caprolactam and 16.0 kg of AH salt aqueous solution (50 wt% aqueous solution) were added to a 70 L autoclave, and 2.48 g of an aqueous HMD solution as a polymerization regulator was added, and the same method as in Example 1 was carried out to obtain a relative viscosity. 4.02. Polyamide resin having a melting point of 192 °C. This is called polyamine resin PA-5.

(Comparative Example 3: Production of Polyamine Resin (PA-6))

Into a 70 L autoclave, 16.0 kg of ε-caprolactam and 4.0 kg of 12-aminododecanoic acid were added, and 10.58 g of an aqueous HMD solution as a polymerization regulator was added, and the same method as in Example 1 was carried out to obtain a relative viscosity. 4.15. Polyamide resin having a melting point of 196 °C. This is called polyamine resin PA-6.

(Comparative Example 4: Production of Polyamine Resin (PA-7))

In a 70 L autoclave, 15.6 kg of ε-caprolactam was added, and an aqueous solution (50 wt% aqueous solution) of AH salt (a salt obtained by adding a molar amount of adipic acid such as hexamethylenediamine to an aqueous solution of hexamethylenediamine) was added. 2.2 kg of Hg and 12-aminododecanoic acid and 9.39 g of an aqueous HMD solution as a polymerization regulator were added, and a polyamine resin having a relative viscosity of 4.29 and a melting point of 184 ° C was obtained in the same manner as in Example 1. This is called polyamine resin PA-7.

(Comparative Example 5: Production of Polyamine Resin (PA-8))

An aqueous solution (50 wt% aqueous solution) of 15.6 kg of ε-caprolactam and AH salt (a salt obtained by adding a molar amount of adipic acid such as hexamethylenediamine to hexamethylenediamine) was added to a 70 L autoclave. In the same manner as in Example 1, 6.0 kg of 6.0 kg of 12-aminododecanoic acid and 6.07 g of an aqueous HMD solution as a polymerization regulator were added to obtain a polyamide resin having a relative viscosity of 4.47 and a melting point of 185 °C. This is called polyamine resin PA-8.

(Comparative Example 6: Production of Polyamine Resin (PA-9))

14.0 kg of ε-caprolactam and 12.0 kg of AH salt aqueous solution (50 wt% aqueous solution) were added to a 70 L autoclave, and the same method as in Example 1 was carried out except that the HMD aqueous solution was not used, and the relative viscosity was 4.06. Polyamide resin at 178 °C. This is called polyamine resin PA-9.

(Example 4: Production of a film)

A T-die forming apparatus (mold width: 300 mm) manufactured by Bravo Co., Ltd. was used under the conditions of a molding temperature of 250 ° C, a first cooling roll 30 ° C, and a second cooling roll of 27 ° C to obtain the aggregate obtained in Example 1. A single layer of unstretched film of a thickness of 50 μm and 100 μm of a polyamide resin (PA-1). The obtained single-layer unstretched film having a thickness of 100 μm was cut into a longitudinal direction of 92 mm and a lateral direction of 92 mm, and this was placed in an extending groove of a biaxial stretching machine BIX-703 (manufactured by Iwamoto Seisakusho Co., Ltd.) adjusted to a temperature of 100 ° C at 100 ° C. After preheating for 60 seconds, the extrusion direction at the time of forming the T-die and the two directions in the right-angle direction are extended by 3.0 times or 3.4 times at a deformation speed of 150 mm/sec. Heat treatment was carried out for 1 minute in a heated air of 100 ° C to obtain a simultaneous biaxially stretched film. The shrinkage and puncture strength were measured using a simultaneous biaxially stretched film of an unstretched film having a thickness of 100 μm. Further, the oxygen permeability coefficient was measured using an unstretched film having a thickness of 50 μm.

(Examples 5 to 6, Comparative Examples 7 to 12)

An unstretched film and a simultaneous biaxially stretched film were obtained in the same manner as in Example 4 except that the polyamide resin represented by Table 2 was used instead of the polyamide resin (PA-1). The shrinkage and puncture strength were measured using a simultaneous biaxially stretched film in the same manner as in Example 4, and the oxygen permeability coefficient was measured using an unstretched film.

The results are summarized in Tables 1 and 2. Further, in Examples 1 to 3, Comparative Example 1, Comparative Example 2, and Comparative Example 4 to Comparative Example 6, the content ratio of the unit 1 to the total of the unit 1, the unit 2, and the unit 3 was determined. On the other hand, Comparative Example 3 does not include the unit 1, the unit 2, and the unit 3, and is not an object.

The polyimide films of Examples 4 to 6 had good shrinkability, puncture strength after heat treatment, and deep drawability. On the other hand, the polyimide films of Comparative Examples 7 to 12 exhibited a tendency to be inferior in any of the items of shrinkage strength, puncture strength after heat treatment, and deep drawability. Specifically, it is as follows.

Comparative Example 7 is a polyimide film obtained by using the polyamide resin of Comparative Example 1. In the polyamide resin of Comparative Example 1, since the amount of the unit 1 was 80% by weight, the polyamide film of Comparative Example 7 was inferior in shrinkability and deep drawability.

Comparative Example 8 is a polyimide film obtained by using the polyamide resin of Comparative Example 2. In the polyamide resin of Comparative Example 2, since the amount of the unit 1 was 60% by weight, the puncture strength (especially the puncture strength after heat treatment) was inferior.

Comparative Example 9 is a polyimide film obtained by using the polyamide resin of Comparative Example 3. Since the polyamide resin of Comparative Example 3 does not have the unit 2 and the unit 3, the shrinkage property is particularly inferior.

Comparative Examples 10 and 11 are polyimide films obtained by using the polyamide resins of Comparative Examples 4 and 5. In the polyamide resin of Comparative Example 4, since the amount of the unit 1 was 80% by weight or more, the polyamide film of Comparative Example 10 was inferior in shrinkability and deep drawability. Similarly, the polyamide film of Comparative Example 11 was inferior in shrinkability. Further, the polyamine resins of Comparative Examples 4 and 5 were obtained by containing a unit derived from 12-aminododecanoic acid and using a polyamine resin derived from a 12-aminododecanoic acid unit. The polyimide films of Comparative Examples 10 and 11 had higher oxygen permeability coefficients than the polyimide films of Examples 4 to 6.

Comparative Example 12 is a polyfluorene obtained by using the polyamide resin of Comparative Example 6. Amine film. Here, in the polyamide resin of Comparative Example 6, the concentration of the terminal amine group of the polyamide resin was equal to or less than the carboxyl group concentration of the terminal of the polyamide resin. Therefore, the polyimide film of Comparative Example 12 had poor puncture strength with respect to Example 5 of the polyamine resin of Example 2 in which the contents of the units 1 to 3 were the same.

The measured values shown in Tables 4 and 5 were measured by the following methods.

9) Nodule strength: The tensile tester was a TENSILON universal material testing machine RTA-10KN manufactured by A and D. The rope was wound with one monofilament, and both ends were placed on the head of the tensile tester. The tensile strength was evaluated at a rate of 200 mm/min under an environment of 23 ° C and humidity adjustment to 50% RH. The unit of intensity is expressed in cN/dTex. In order to calculate the cross-sectional area, the weight per 5 m was measured and converted into a weight (Tex) per 1000 m and used for calculation of the strength.

10) Formability: The monofilament is formed so that no bubbles or the like occurs inside the roundness and the monofilament, and no fracture occurs as an index during elongation, and the occurrence of fracture is judged as ×, and no fracture occurs. It was judged as ○, and the formability of the monofilament was evaluated.

11) Transparency: The monofilament was placed on a black paper on which white lines were drawn, and visually confirmed, and the transparency was evaluated as follows.

○: The white line can be clearly seen through the monofilament

△: The outline of the white line can be seen faintly through the monofilament

×: The wheel of the white line is not visible through the monofilament.

Comparative Example 13: Production of polyamine resin (PA-10)

20.0 kg of ε-caprolactam was added to a 70 L autoclave, and the same procedure as in Example 1 was carried out to obtain a polyamide resin having a relative viscosity of 4.05 and a melting point of 220 °C. This polyamine resin is referred to as PA-10.

(Example 7: Production of monofilament)

The pellet was melted by a single-axis extruder, and the polyamine resin PA-2 obtained in a 70-liter autoclave was extruded to a setting of 15 using a mold having a set temperature of 260 ° C and a diameter of 6 mm. In a water bath of °C, it is allowed to cool and solidify. In the first extension, a 4-fold extension was performed with steam heating at 100 °C. Next, in the second extension, heating was performed at 200 ° C by hot air to perform double stretching. The total is extended to 6 times. Then, it was heat-fixed by hot air of 250 ° C, and relaxed by about 5% to obtain a monofilament sample. The obtained monofilament had a diameter of 2.0 mm. Formability, nodule strength, and transparency were evaluated using the obtained monofilament.

(Example 8, Comparative Examples 14 to 16)

A silk-based 2 mm monofilament was obtained in the same manner as in Example 7 except that the polyamine resin (PA-2) was replaced with the polyamine resin shown in Table 4. Nodular strength, transparency, and moldability were measured in the same manner as in Example 7.

(Examples 9 to 10, Comparative Examples 17 to 19)

A silk 3 mm monofilament was obtained in the same manner as in Example 7 except that the polyamide resin (PA-2) shown in Table 5 was used instead of the polyamide resin (PA-2), and the diameter of the mold was 10 mm. . Nodular strength, transparency, and moldability were measured in the same manner as in Example 7.

The results are organized in Tables 3, 4 and 5.

The polyamide monofilament systems of Examples 7 to 10 had good knot strength, transparency, and formability with respect to Comparative Examples 15 to 20 having the same wire diameter. On the other hand, the polyamine monofilaments of Comparative Examples 7 to 12 showed a tendency to be inferior in any item of knot strength, transparency, and formability. Specifically, it is as follows.

Comparative Examples 14 and 17 are polyamidamine monofilaments obtained by using the polyamide resin of Comparative Example 1. In the polyimide resin of Comparative Example 1, since the amount of the unit 1 was 80% by weight, the polyamine amine filaments of Comparative Examples 14 and 17 were inferior in knot strength and transparency.

Comparative Examples 15 and 18 are polyamidamine monofilaments obtained by using the polyamide resin of Comparative Example 3. Since the polyamide resin of Comparative Example 13 did not have the unit 2 and the unit 3, the polyamine monofilaments of Comparative Examples 15 and 18 were particularly inferior in knot strength.

Comparative Examples 16 and 19 are polyamidamine monofilaments obtained by using the polyamide resin of Comparative Example 13. Since the polyamide resin of Comparative Example 13 contained only the unit 1, the polyimide of the comparative examples 16 and 19 had poor transparency and further inferior formability. In particular, the polyamide polyamide filaments of Comparative Examples 16 and 19 were inferior in formability, and thus the measurement of the knot strength could not be performed.

[Probable use of industry]

According to the present invention, it is possible to provide more excellent shrinkage of a film, puncture strength and deep drawability after wet heat treatment, and impart nodular strength, transparency, tensile strength after wet heat treatment and formability of a monofilament. The polyamide resin of the molded article and the molded article using the polyimide resin. The molded article containing the polyamine resin composition of the present invention can be used for the use of a molded article of a conventional polyamide resin composition, and can be used for a film for food packaging, an automobile member, a computer, a related machine, or an optical machine. Among the wide range of applications such as components, electrical/electronic equipment, information/communication equipment, precision machinery, civil engineering/construction supplies, medical supplies, and household goods, it is particularly advantageous for the use of films and filaments for food packaging.

Claims (13)

A polyamidamide resin containing a unit derived from ε-caprolactam and/or ε-aminohexanoic acid (hereinafter also referred to as "unit 1") and a source of adipic acid (hereinafter, Also referred to as "unit 2"), and a unit derived from its own diamine (hereinafter also referred to as "unit 3"), wherein the polyamine resin has a tail amine group concentration higher than that of the aforementioned polyamine The carboxyl group concentration of the tail end of the resin is larger, and the unit 1 is more than 60% by weight and less than 80% by weight with respect to the total amount of the unit 1, the unit 2, and the unit 3, and has the following (1) and (2) Characteristics: (1) The relative viscosity (η r) of the above polyamine resin measured in 96% by weight of sulfuric acid at a polyamine concentration of 1% by weight and a temperature of 25 ° C is 3.4 or more; and (2) The carboxyl group concentration at the tail end is 2.00 to 3.00 × 10 ^-5 eq/g. The polyamine resin according to claim 1, which does not contain a unit derived from a component selected from 12-aminododecanoic acid and ω-lauric acid. The polyamide resin according to claim 1 or 2, which consists essentially of only unit 1, unit 2 and unit 3. The polyamine resin according to claim 1 or 2, wherein the tail amine group concentration is from 2.30 to 3.30 x 10 ^-5 eq/g. The polyamide resin according to claim 1 or 2, wherein the difference between the tail amine group concentration and the terminal carboxyl group concentration is 0.05 to 1.0 × 10 ^-5 eq/g. A molded article containing any of the first to fifth items of the patent application scope A polyamine resin as described. An unstretched polyamidamine film comprising the polyamidamide resin according to any one of claims 1 to 5. An extended polyamidamine film obtained by extending the unstretched polyamidamine film described in claim 7 of the patent application. The unstretched polyamide film as described in claim 7 is a film for food packaging. The extended polyamide film as described in claim 8 is a film for food packaging. A laminated film comprising the unstretched polyamidamine film described in claim 7 of the patent application. A laminated film comprising the extended polyamine film described in claim 8 of the patent application. A polyamidamine monofilament comprising the polyamidamide resin according to any one of claims 1 to 5.